Acid-amine condensation products



Pussies Mar. 7, 1939 UNlTED STATE ACID-AMINE ooNnsNsA'rroN PRODUCTS -Almon G. Hovey, Pleasant Ridge, and Theodore S. Hodgins, Detroit, Mich., assignors to Helmuth Reichhold, Detroit, Mich., doing business as Beichhold Chemicals I No Drawing.

ZClaims.

The invention relates to acid-amine condensa-. tion products, and the process of making the same.

The claims of the present application are directed to resinous condensation products formed by fusing benzoylbenzoic acid and an organic June 10, 1937.

There are a large number of patents on urea condensation products but practically all of them cover tedious delicate processes requiring very careful control of such conditions as pH and temperature. The ingredients must be carefully reacted in a certain prescribed order and very specific directions followed or else the product is likely to go over to a useless white insoluble precipitate, or else to a gel. covering urea resins are intended for moulding purposes. The preparation of surface coating resins from urea is much more difficult than the preparation of moulding compositions. coating resins must be miscible with the commonly used paint, varnish and lacquer ingredi= ents, and require skill not given in any publication heretofore; Furthermore, in the manufacture of urea resins it has not been possible to make products which are as easy to cook or as foolproof in manufacturing as the alkyd resins. It has not been possible, to make resins by fusing urea or other amines with other reactive ingredients at relatively high temperatures because gelation inevitably takes placeat too rapid a rate even for a rough control.

A fusion method would be highly desirable because it would avoid the tendency towards precipitation when an aqueous formaldehyde solution is used and it would avoid dangerous formation of steam should the reaction run away. Furthermore, the fusion method would allow the use of higher temperatures similar to those used in alkyd resin formation and with a much better chance of obtaining resinification than if the reaction were carried onin an aqueous solution. 1

We have found how to make resins by such a fusion process, and we have found that not only urea may be used, but a large variety of amines, including mono-amines, which hithertofore have Most of these patents- Surface Application February 2, 1938, Serial No. 188.392

s PATENT osrics been regarded as inoperative or unsuitablefor any type of resin formation. Mono-amines and other amines may have been suggested as modifying agents for resins, but have never been considered as the basic resin-forming ingredients. 5 In our process, no control of pH is necessary, the resinification taking place under as orderly conditions as in the case of the alkyd resins, instead, of requiring the meticulous control of artificial conditions which is necessary in the case of the 10 urea-formaldehyde processes which have beenhithertofore described. It is not necessary that a solvent or dispersing medium be present; our operations consist only of fusing the ingredients, i. e., the acid and amine. Thus, the apparatus 15 required for carrying out our process is less com- The obvious simplicity of our process makes it especially desirable. The increasing availability and potential plicated and less expensive.

- low cost of producing many a'min process even more desirable.

eral reaction:

Where R, R, R"=alkyl or aryl groups.

Y=a group such as n R1=segment of hydrocarbon structure (alk lene or arylene) e.

4 etc. d =any functional group, such as es makes our Resins resins -der the classification of the based on the variation of the acidic component with the assumption that amines are operative equivalents, i. e., that the trivalent nitrogen becomes pentavalent.

1. Ketonic acid+amineketacine resins. 2. Unsaturated acid+amine unacine resins. 3. Dibasic acid+aminedibacine" resins.

4. Hydroxy acid+amine hydracine" resins.-

These resins which we are describing are not to be confused with the resins such as are described in Weisberg and Greenwald U. S. Patentv hydric alcohol. Triethanolamine and phthalic anhydrld'e should form a resin in exactly the same way and according to the same principle as-does glycerol and phthalic anhydride' as described'by Kienle and Hovey (Journal of 1 The American Chemical Society, volume 501, page 512, (1929) Wehave found that amines without any hydroxyl groups form resins with the organic acids of the generic formula R-d R2-'COOH (as mentioned previously) this being an entirely unexpected result which is entirely outside the classification of alkyd resins, the definition of an alkyd resin by Kienle and Ferguson being a "product of polybasic acids and polyhydric alcohols" (Industrial and Engineering Chemistry, volume 21, pages 349-52, (1929) This application is one of a series in which resins made from amine and various types of organic acids are described. The present applithis application shall be termed"ketacine resins.

The ketonic acids which form ketacine resins with amines according to our invention come un- I following general formula:

R.CO.R'.COOH

Where R =an alkyl or aryl group, and w R'=an alkylene or arylene group (carbon atom length may be 0 to 11)..

Specific examples of this general formula are:

Py'ruvic acid CH3.CO.COOH Aceto-acetic' acid CHa.CO.CH2.COOH Benzoylbenzoic acid CcHs.CO.CaHs-.COOH Benzophenone-dicarboxylic acid CcHs.CO.CsHs (COOH) a Benzoyl acrylic acid CsHaCQCHtCECOOH Paramethylisopropylorthobenzoylbenzoic acid CaHa (CH3) (CaH1).CO.'CuH4.COO H The following table giving many general examples of how various types of resins may be pre-' 'One mol of urea is reacted with one mol 0 and the colorof the resinous product changed These reactions fall into'four general classes Gnmm. Exu lrrls Table I I. Pyruvic acid +urea- .red-orange resin.

Pyruvic acid isobutyl amineyelloworange resin. 'Pyruvic acid anilineyellow-orange resin. Pyruvic acid+ hexamethylene tetramine red-orange resin.

Pyruvic acid formamide-wed-oranse resin; 10

, Pyruvic acid succinimideyellow-orang'e resin. Pyruvic acid thioureaeblack resin.

Pyruvic acid triethanolamine-mrange- 15 brown resin. II. Aceto-acetic acid urea-*yellow resin.

. Benzoylbenzoic acid urea yellow resin.

Benzoylbenzoic acid isobutylamine-flight straw colored resin.

Benzoylbenzoic acid acetamidegreen res- 2 in. Benzoylbenzoic acid aniline yelloworange resin. Benzoylbenzoic acid hexamethylene tetraminedark brown resin. Benzoylbenzoic acid formamidegreen resin. Benzoylbenzoic acid succinimidebrown resin.

Benzoylbenzoic acid thiourea brown resin.

Benzoylbenzoic acid monoamylamine water-white resin.

Benzoylbenzoic acid diamylamine brown resin.

Benzoylbenzoic acid triamylamineyellow 3 resin. Benzoylbenzoic acid monomethylamine water-white resin. Benzoylbenzoic acid -I-' dimethylamine water-white resin. Benzoylbenzoic acid trimethylaminwwater-white resin. Benzoylbenzoic acid py dine water-white resin.

, 4 Benzoylbenzoic acid dimethylanilinewater-white, sticky balsam resin. Paramethylisopropylorthobenzoylbenzoic acid urea-flight straw colored resin.

V. Benzoyiacrylic acid ureareddish-brown 50 resin. Benzoylacrylic acid isobutylamine-mrange balsam resin. Benzoylaorylic acid aniline-wellow-orange resin.

ter-white resin. Benzophenonedicarboxylic acid isobutylamine red resin.

. 60 'The following are specific examples of hown benzoylbenzoic acid at C. The ingredients were heated to 150 C. in 10' minutes and then ,held at 150 C. for-30 minutes or longer. As the reaction proceeded the acid number decreased mtion. This is shown by the following table:

. 5 Benzophenonedicarboxyllc acid urea-wa- Tm! II Change in acid number and cure of a resin formed from one mol benzowl bensoic acid and one mol urea 'limeat1500.' 3 8 Ours" Oolorofproduot SQNfldB 164 26' Water-white. 160 14 Do.

146 12 Do. 132 9 Pole yellow. 116 8 Yellow. 98 ii Do. 88 2, Do.

F10 minutes were reouiredto fuse the materials and obtain 150 0.

"Hot plate temperature 200' c.

when means 'are used to protect the color which are known to the art, a much lighter colored product is obtained. a

. Example II' To one mol of benzoyl benzoic acid, two moisof isobutylamine are added. An exothermic reaction takes place which warmsthe mixture of ingredients to approximately 70C. These ingradients are allowed to react from. their own ume toone volume, but when it cooled the resin 60 precipitated from solution.

When this material was thinned witlrbutanol, it formed a very stable solution which blended with practically all of the commercial types of alkyd resins even if. they were already cut 50% iii-mineral spirits.-

This family of resins made from ketonic acids and amines maybe modified by other ingredients to vary the properties in much the same waythat alkyd resins made from polyb'aslc acidsand poly-,

I hydric alcohols have been modified with the fatty On the other hand, if one should use ketacine resins to modify other resinous productsgthese uses of the "ketacine" resins are. to'be considered '00 as applications of this invention and also includ ed by it. As an example for a use of our invention" to modify other resinous productsthe following is cited as illustrative: I

The resin made frombenzoyl bensoic acid and isobutylamine as shown in Example 11 is used in combination with the urearformaldehyde' condensation process. 200 parts of the resin prepared as in Example 11, and 62 parts oL-formalde- .hyde (commercial solution 37-40%) and'30 parts of urea are reacted together. First the formaldehyde is-added to the resinmade'from bens'oyl benzoic acid and isobutylamine' and a cloudy white precipitation occurs during the stages of reaction, but this soon clears up between 50-60? C. When the formaldehyde is added the temperature rises from room temperature to 50- 70 C. Uponndding 30 parts of urea the solution became somewhat cloudy and viscous, but it becomes clear upon gradually increasing the temperature to 95 C. and holding at this temperature. The material becomes more and more viscous and continues to remain clear. When the desired viscosity is obtained the material may be thinned'with butanol to a 60% solution. This clear straw coloredvlscous solution in butanol is miscible with all types of commercial alkyd resin solutions sucl'. as the oil or oil acid modified types of polybasic acid-polyhydric resins in solution form, using hydrocarbon solvents, either of the aromatic or aliphatic types. The product is soluble in butanoL xylol or toluol to'practically any proportion and soluble to approximately equal parts by volume in mineral spirits. This modified nna-formaldehyde condensation product bakes out to a clear and hard film either by itself or in combination with the oil or oil acid modified alkyd resins showing complete compatibility of the resin even in the baked fllm where the solvents have had a chance to evaporate.

Products made along orthodox varnish and lacquer technology with resins of the "ketacine" family are to be considered as applications of this resin family and to .be covered by the scope of this invention. It is to be further understood 'that' certain catalysts maybe used to promote further resiniflcation of theseingredients or to I have found it especially helpful to introduce such a catalyst. An instance of this is in the case of isobutylamine and pyruvic acid, in which the resiniflcationis speeded up materially. We an- ,ticipate that any process which undertakes the simultaneous reduction of a nitro compound 'to an amine and at, the same time resinifying the resulting amine with a ketonic acid to be within .the scope of our invention. For example, wehave shown that aniline, the reduction product of nitrobenzene can form aresin with ketonic acid.

In surface coatings such as lacquers and varnishes these resins, on account of their adhesive properties, increase the value of surface coatings, especially lacquers, where they increase adhesion, toughness and hardness of the resulting product. The usefulness of these products is not limited to surface coating materials as it extend into plastic moulding compounds as well and particularly into-rubber since they reduce the porosity of rubber andincreas'e the adhesion and tend to act as antioxidants and, in the case of the thiourea' cipal reacting ingredients.

2. A process of preparing 'a resinous condensation product which comprises fusing 'benzoylbenzoic acid and an organic amine, said acid and i amine constituting ients.

- 2. ALMON G. TEBODORES. HODGINBJ the principal ingred 0 

